EP3713870A2 - Procédé et appareil pour la production combinée d'hydrogène et de dioxyde de carbone à partir d'un mélange d'hydrocarbures - Google Patents
Procédé et appareil pour la production combinée d'hydrogène et de dioxyde de carbone à partir d'un mélange d'hydrocarburesInfo
- Publication number
- EP3713870A2 EP3713870A2 EP18867317.2A EP18867317A EP3713870A2 EP 3713870 A2 EP3713870 A2 EP 3713870A2 EP 18867317 A EP18867317 A EP 18867317A EP 3713870 A2 EP3713870 A2 EP 3713870A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- permeate
- hydrogen
- carbon dioxide
- synthesis gas
- membrane system
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 215
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 107
- 239000001257 hydrogen Substances 0.000 title claims abstract description 85
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 85
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 70
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 53
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 35
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
- 239000000203 mixture Substances 0.000 title claims abstract description 18
- 230000008569 process Effects 0.000 title claims abstract description 18
- 239000007789 gas Substances 0.000 claims abstract description 95
- 239000007788 liquid Substances 0.000 claims abstract description 20
- 239000012466 permeate Substances 0.000 claims description 73
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 72
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 66
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 64
- 239000012528 membrane Substances 0.000 claims description 64
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 57
- 230000015572 biosynthetic process Effects 0.000 claims description 56
- 238000003786 synthesis reaction Methods 0.000 claims description 56
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 35
- 239000001294 propane Substances 0.000 claims description 33
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 32
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 30
- 239000005977 Ethylene Substances 0.000 claims description 30
- 239000002912 waste gas Substances 0.000 claims description 27
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 22
- 238000001179 sorption measurement Methods 0.000 claims description 22
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 21
- 239000012535 impurity Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 150000002431 hydrogen Chemical class 0.000 claims description 18
- 238000002407 reforming Methods 0.000 claims description 17
- 238000007906 compression Methods 0.000 claims description 16
- 230000006835 compression Effects 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000011144 upstream manufacturing Methods 0.000 claims description 12
- 238000009833 condensation Methods 0.000 claims description 11
- 230000005494 condensation Effects 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 11
- 238000004821 distillation Methods 0.000 claims description 9
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 230000001590 oxidative effect Effects 0.000 claims description 8
- 238000011084 recovery Methods 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 239000000446 fuel Substances 0.000 claims description 7
- 238000005371 permeation separation Methods 0.000 claims description 4
- 239000012530 fluid Substances 0.000 claims description 2
- 230000004907 flux Effects 0.000 claims description 2
- RXXCIBALSKQCAE-UHFFFAOYSA-N 3-methylbutoxymethylbenzene Chemical compound CC(C)CCOCC1=CC=CC=C1 RXXCIBALSKQCAE-UHFFFAOYSA-N 0.000 claims 1
- MDOAAHGPXOGVQG-UHFFFAOYSA-N ethene;propane Chemical group C=C.CCC MDOAAHGPXOGVQG-UHFFFAOYSA-N 0.000 claims 1
- 238000000746 purification Methods 0.000 description 10
- 239000002699 waste material Substances 0.000 description 6
- 101150008822 rpsA gene Proteins 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 238000009434 installation Methods 0.000 description 4
- 238000000629 steam reforming Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 239000003517 fume Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000008246 gaseous mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920002480 polybenzimidazole Polymers 0.000 description 2
- 102100027271 40S ribosomal protein SA Human genes 0.000 description 1
- 101000694288 Homo sapiens 40S ribosomal protein SA Proteins 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004693 Polybenzimidazole Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000011143 downstream manufacturing Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000009418 renovation Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/48—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents followed by reaction of water vapour with carbon monoxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
- B01D53/047—Pressure swing adsorption
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/225—Multiple stage diffusion
- B01D53/226—Multiple stage diffusion in serial connexion
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/229—Integrated processes (Diffusion and at least one other process, e.g. adsorption, absorption)
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0006—Controlling or regulating processes
- B01J19/0013—Controlling the temperature of the process
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/24—Stationary reactors without moving elements inside
- B01J19/245—Stationary reactors without moving elements inside placed in series
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/36—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using oxygen or mixtures containing oxygen as gasifying agents
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- C—CHEMISTRY; METALLURGY
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/501—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/506—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification at low temperatures
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/50—Carbon dioxide
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
- F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
- F25J3/0204—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the feed stream
- F25J3/0223—H2/CO mixtures, i.e. synthesis gas; Water gas or shifted synthesis gas
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
- F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
- F25J3/0228—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream
- F25J3/0252—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream separation of hydrogen
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
- F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
- F25J3/0228—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream
- F25J3/0266—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream separation of carbon dioxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2256/00—Main component in the product gas stream after treatment
- B01D2256/16—Hydrogen
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
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- B01D2257/7022—Aliphatic hydrocarbons
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- B01D2257/7025—Methane
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- B01D2257/702—Hydrocarbons
- B01D2257/7027—Aromatic hydrocarbons
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- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00002—Chemical plants
- B01J2219/00027—Process aspects
- B01J2219/0004—Processes in series
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- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
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- C01B2203/025—Processes for making hydrogen or synthesis gas containing a partial oxidation step
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- C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
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- C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
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- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/046—Purification by cryogenic separation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/0475—Composition of the impurity the impurity being carbon dioxide
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/048—Composition of the impurity the impurity being an organic compound
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/0495—Composition of the impurity the impurity being water
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/14—Details of the flowsheet
- C01B2203/148—Details of the flowsheet involving a recycle stream to the feed of the process for making hydrogen or synthesis gas
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- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2200/00—Processes or apparatus using separation by rectification
- F25J2200/02—Processes or apparatus using separation by rectification in a single pressure main column system
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2200/00—Processes or apparatus using separation by rectification
- F25J2200/70—Refluxing the column with a condensed part of the feed stream, i.e. fractionator top is stripped or self-rectified
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2205/00—Processes or apparatus using other separation and/or other processing means
- F25J2205/02—Processes or apparatus using other separation and/or other processing means using simple phase separation in a vessel or drum
- F25J2205/04—Processes or apparatus using other separation and/or other processing means using simple phase separation in a vessel or drum in the feed line, i.e. upstream of the fractionation step
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- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2205/00—Processes or apparatus using other separation and/or other processing means
- F25J2205/40—Processes or apparatus using other separation and/or other processing means using hybrid system, i.e. combining cryogenic and non-cryogenic separation techniques
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2205/00—Processes or apparatus using other separation and/or other processing means
- F25J2205/60—Processes or apparatus using other separation and/or other processing means using adsorption on solid adsorbents, e.g. by temperature-swing adsorption [TSA] at the hot or cold end
- F25J2205/64—Processes or apparatus using other separation and/or other processing means using adsorption on solid adsorbents, e.g. by temperature-swing adsorption [TSA] at the hot or cold end by pressure-swing adsorption [PSA] at the hot end
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- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2205/00—Processes or apparatus using other separation and/or other processing means
- F25J2205/80—Processes or apparatus using other separation and/or other processing means using membrane, i.e. including a permeation step
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2245/00—Processes or apparatus involving steps for recycling of process streams
- F25J2245/02—Recycle of a stream in general, e.g. a by-pass stream
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/20—Capture or disposal of greenhouse gases of methane
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
Definitions
- the present invention relates to a process for the combined production of hydrogen and carbon dioxide from a hydrocarbon mixture in which the hydrocarbon mixture is reformed to produce a synthesis gas containing hydrogen, monoxide of carbon, carbon dioxide and at least one hydrocarbon which is cooled, then enriched in hydrogen (H 2 ) and carbon dioxide (CO 2 ), optionally dried, and treated in a pressure modulation absorption unit (PSA) ) of hydrogen purification to produce hydrogen (the drying may precede or follow the purification), the waste being treated to capture CO 2 . It also relates to an installation capable of implementing the method.
- PSA pressure modulation absorption unit
- CO 2 emissions As climate change is one of today's major environmental problems, reducing greenhouse gas emissions, and in particular reducing CO 2 emissions, is one of the major challenges facing man.
- One of the essential sources of CO 2 emissions is the burning of fossil fuels.
- one of the methods used is the capture of carbon dioxide compressing and cooling the waste gas from the hydrogen purification unit by pressure swing adsorption (PSA H 2 ), so as to liquefy a fraction of the carbon dioxide contained in said waste gas.
- PSA H 2 pressure swing adsorption
- This liquid carbon dioxide can then be transported, stored, processed or used as needed. It is desirable for the operator of the facility to recover the non-condensed gases resulting from this operation of CO2 capture by compression and purification or CPU (compression and purification unit of the English).
- the method implements PSA waste gas compression steps, followed by a drying step (the drying can, as described in WO2008 / 017783, be carried out upstream of the PSA) with recovery of the carbon dioxide.
- carbon via a cryogenic purification unit (CPU).
- the incondensable gases from the CPU are treated with a membrane allowing the hydrogen to permeate.
- the hydrogen is returned upstream of the process, at the inlet of the PSA to increase the production of hydrogen of the plant, the residual gas from the membrane being used in the reforming stage, as fuel and or as a charge for feeding the reforming.
- the same document proposes to carry out a step of removal of heavy impurities by adsorption prior to the partial condensation step of the waste gas.
- adsorption system for removing a constituent such as propane, as it does not exist for ethane either.
- Another solution would be to vaporize the CO2-rich product liquid resulting from the partial condensation of the waste gas, to heat it to a temperature of the order of 400 to 500 ° C, to inject oxygen and to carry out an oxidation.
- catalytic system to remove such hydrocarbons as ethane and propane, then to cool and liquefy this CO2, to carry out a new distillation to remove oxygen so as to produce food grade liquid carbon dioxide which can then be transported and stored.
- this alternative is both expensive and complex.
- the CO2 must be recompressed at the outlet of the membrane, whereas according to the invention, a very high permeate pressure is maintained which is compatible with a condensation of CO2 in the CPU.
- the permeate is close to atmospheric pressure, which does not allow it to be condensed directly since the CO2 can be in the liquid state only at a pressure greater than 519 kPa, ie 5, 19 bar abs or 0.519 MPa.
- the objective of the present invention is therefore to meet the need to produce food grade CO2 without unduly complicating the installation. It consists in installing a membrane separation stage from which a permeate enriched in hydrogen and carbon dioxide is recovered, in which the quantities of impurities, in particular ethane, ethylene, propane and propene, are considerably reduced. Although this operation reduces the partial pressure of CO2 in the gas being partially condensed, it simplifies the process. Moreover, incondensables resulting from the partial condensation are richer in hydrogen and they do not need to be purified by a membrane. They can be directly recycled upstream of the PSA hh to increase the hydrogen production of the hydrogen. unit or be treated in a separate H2 PSA.
- a step (h) for permeation separation of the flow of the waste gas in a first membrane system for obtaining a permeate depleted in at least one of the following hydrocarbons: ethane, propane, ethylene, propene, benzene, methanol and enriched with carbon dioxide and hydrogen and a non-permeate enriched in at least one of the following hydrocarbons: ethane, propane, ethylene, propene and depleted of carbon dioxide and hydrogen, the permeate having a partial pressure of carbon dioxide greater than 519 kPa, preferably greater than 1000 kPa, and
- step (i) of partial condensation and / or distillation of said permeate for obtaining a CO2-rich liquid stream and a waste gas stream.
- step (h) there is no permeate compression step between steps (h) and (I). the non-permeate of step (h) is separated in a second membrane system.
- step (h) the non-permeate of step (h) is partially condensed.
- the waste gas stream is sent to the adsorption unit by pressure modulation.
- step (h) At least a part of the non-permeate of step (h) or a gas derived from this non-permeate is sent to the reforming or partial oxidation stage, as fuel for a burner of this step.
- step (h) At least a part of the non-permeate of step (h) or a gas derived from this non-permeate is sent to the reforming or partial oxidation stage as feed gas.
- the first and / or second membrane system removes at least one of the following hydrocarbons: ethane, propane, ethylene, propene, benzene, methanol so that at least 80%, or even at least 90% of the at least one hydrocarbon feeding the membrane system is found in the non-permeate of the first and / or second membrane system.
- the method may comprise a compression step in a compressor upstream of the first membrane system.
- a fluid derived from the non-permeate of the first membrane system is recycled upstream of the compressor.
- the CO2-rich liquid stream obtained is of food grade.
- the invention provides a process for the combined production of hydrogen and carbon dioxide from a hydrocarbon mixture comprising at least the following steps:
- a compression step (h) (step (g) may also be carried out after the compression step) and purification of the Rpsa flow comprising a first permeation separation phase (membrane) for obtaining an enriched permeate in hydrogen and carbon dioxide and depleted in most impurities and a second phase of obtaining a liquid or supercritical flow rich in CO2 and a waste gas stream RI enriched in hydrogen and
- the drying step (g) can be carried out before the compression step of step (h); when the compression step comprises successive intermediate compressions, the drying can be performed during the compression step, between two intermediate compressions; step (g) can also be performed after the compression step.
- the impurities of which at least one of the following hydrocarbons: ethane, propane, ethylene, propene, benzene, metbanol can be in the synthesis gas from step a) and / or can be produced during the shift step c ).
- an apparatus for the combined production of hydrogen and carbon dioxide from a hydrocarbon mixture comprising:
- synthesis gas originating from an apparatus for reforming or partially oxidizing a hydrocarbon mixture in order to obtain synthesis gas containing at least hydrogen and carbon monoxide, carbon dioxide, methane, water vapor and possibly impurities including at least one of the following hydrocarbons: ethane, propane, ethylene, propene, benzene, methanol with available heat recovery, a conversion reactor (in English "shift") of all or part of the cooled synthesis gas for oxidizing most of the carbon monoxide to carbon dioxide with corresponding production of hydrogen and a synthesis gas enriched in H2 and CO2 and containing impurities including at least one of the following hydrocarbons: ethane, propane, ethylene, propene, benzene, methanol,
- step (c) means for cooling the enriched H2 and CO2 synthesis gas from step (c) with means for removing the condensed water
- PSA H2 pressure modulation adsorption unit
- a first membrane system for permeation separation of the waste gas flow to obtain a permeate depleted in at least one of the following hydrocarbons: ethane, propane, ethylene, propene, benzene, methanol and enriched in carbon dioxide and hydrogen and a non-permeate enriched in at least one of the following hydrocarbons: ethane, propane, ethylene, propene and depleted of carbon dioxide and hydrogen, the permeate having a partial pressure of carbon greater than 519 kPa, preferably greater than 1000 kPa, and means of separation by partial condensation and / or distillation of said permeate for obtaining a CO2-rich liquid stream and a waste gas stream.
- the apparatus may include:
- Figure 1 is a schematic view of a process for the combined production of hydrogen and carbon dioxide as described in WO2006 / 054008 (state of the art).
- Figure 2 is a schematic view of a process for the combined production of hydrogen and carbon dioxide according to a basic configuration of the invention.
- Figure 3 is a schematic view of a method according to the invention which differs from that of Figure 2 in that a second membrane stage improves the recovery of hydrogen and carbon dioxide.
- FIG. 4 is a schematic view of a process according to the invention which differs from that of FIG. 2 in that a second partial condensation and a second membrane stage makes it possible to further improve the recovery of hydrogen and carbon dioxide gas.
- a second partial condensation and a second membrane stage makes it possible to further improve the recovery of hydrogen and carbon dioxide gas.
- FIGS 3A and 4A show in more detail the last part of the respective methods of Figures 3 and 4.
- Figure 1 describes the state of the art in which a hydrocarbon feedstock 1 mixed with water vapor (not shown) feeds a reformer 2 to generate a synthesis gas 3 containing at least carbon monoxide, hydrogen, carbon dioxide, unreacted methane and impurities.
- This steam reforming step is carried out in a steam reforming furnace containing tubes filled with catalysts, the heat required for reforming being provided by combustion.
- the synthesis gas 3 is then cooled to 4, the cooled synthesis gas being then subjected to a shift reaction in 6 during which the carbon monoxide reacts with water (shown but not referenced) to be partly - transformed into hydrogen and carbon dioxide.
- the reaction involved (CO + H2O -> CO2 + H2) is called a gas reaction or a shift reaction.
- This conversion reaction is generally carried out on the synthesis gas at high temperature (HT shift) or at medium temperature (MT shift), a second shift step 6b can be carried out downstream from the previous one, on the synthesis gas partially converted, at lower temperature (in English "low temperature shift”) - this second conversion step 6b is shown in broken lines, it is not mandatory.
- the synthesis gas 7 - at the exit of step 6 or step 6b when step 6 is followed by a step 6b - is enriched in H2 and CO2 and depleted in CO; it is cooled to 8, then the cooled gas 9 is dried at 10 (for example using a TSA type adsorption process) to remove the water molecules and thus obtain a gaseous mixture 1 1 sec - with respect to the downstream treatment gas - which dry gas mixture is then subjected to a separation step in a pressure modulation adsorption unit 12 or PSA H2 to produce a product hydrogen gas stream 16 and a gas stream 14 of PSA waste (waste RPSA).
- the stream 14 is then treated to capture the carbon dioxide; for this, it is compressed (sub-step 13a) so that its pressure is between 20 and 100 bar and it undergoes a substep 13 b of absorption purification so as to remove some heavy impurities such as benzene or benzene.
- a substep 13 b of absorption purification so as to remove some heavy impurities such as benzene or benzene.
- the stream 20 is then subjected to a separation step in a permeation unit 8 through a membrane to produce a gas stream 23 (permeate) enriched in hydrogen (Hii stream) and a gas stream 19 enriched with carbon monoxide and in methane.
- This gaseous stream 19 may, for example, be sent as fuel to the reformer 2.
- the drying of the synthesis gas, upstream and / or downstream of the PSA (not shown) makes it possible to eliminate the water which is detrimental to the smooth running of the reactor. downstream process.
- a hydrocarbon feedstock 1 mixed with steam feeds a reformer 2 to generate a synthesis gas 3 containing at least carbon monoxide, carbon dioxide and carbon dioxide.
- hydrogen, carbon dioxide, unreacted methane and impurities including at least the following hydrocarbons: ethane, propane, ethylene, propene.
- This steam reforming step is carried out in a steam reforming furnace containing tubes filled with catalysts, the heat required for reforming being supplied by combustion.
- the synthesis gas 3 is then cooled to 4, the cooled synthesis gas being then subjected to a shift reaction in 6 during which the carbon monoxide reacts with water (shown but not referenced) to be partly - transformed into hydrogen and carbon dioxide.
- the reaction involved (CO + h1 ⁇ 2G -> CO2 + Fb) is called the water gas reaction or shift reaction.
- This conversion reaction is generally conducted on the synthesis gas at high temperature (HT shift) or at medium temperature (MT shift), a second shift step 8b can be performed downstream of the previous one, on the synthesis gas partially converted, at lower temperature (in English "iow temperature shift") - this second conversion step 6b is shown in broken lines, it is not mandatory.
- the synthesis gas 7 - at the exit of step 6 or step 6b when step 6 is followed by a step 6b - is enriched in H2 and CO2 and depleted in CO; it is cooled to 8, then the cooled gas 9 is dried at 10 (for example using a TSA type adsorption process) to remove the water molecules and thus obtain a gaseous mixture 1 1 sec - with respect to the downstream treatment gas - which dry gas mixture is then subjected to a separation step in a pressure modulation adsorption unit 12 or PSA H2 to produce a gaseous stream 16 of hydrogen produced and a gas stream 14 of PSA waste (residual Rpsa).
- the stream 14 is then treated to capture the carbon dioxide; for this, it is compressed in a compressor 13 so that its pressure is between 20 and 100 bar to produce the gas 17. It can undergo a substep of adsorption purification so as to remove some heavy impurities such as benzene or methanol. Then, it is separated in a membrane system 8 to produce a permeate enriched with carbon dioxide and hydrogen and a non-permeate depleted of carbon dioxide and hydrogen and containing at least 90% of the at least one hydrocarbon present. in the gas 17.
- the permeate 20, having a CO2 partial pressure of at least 519 kPa is not compressed and undergoes one or more successive condensation / separation steps in the CPU 21 to obtain a liquid flow.
- the stream 23 is returned to the adsorption unit 12 to separate it with the gas 1 1.
- the non-permeate 19 enriched in at least one of the following hydrocarbons: ethane, propane, ethylene, propene and depleted of carbon dioxide and hydrogen is sent as fuel to the furnace 2.
- the membrane of the membrane system 17 can operate between ambient temperature of 100 ° C, preferably around 80 ° C, for example between 70 and 90 ° C.
- the membrane may be a polymeric membrane capable of separating hydrogen which may be a polyamide, polyaramid, polybenzimidazoles, mixture of polybenzimidazole and polyimides.
- the non-permeate 19 of the first membrane system 17 is sent to a second membrane system 24.
- the non-permeate 19 enriched in at least one of the following hydrocarbons: ethane, propane, ethylene, propene and depleted in carbon dioxide and in Hydrogen separates in the second membrane system 24.
- the permeate 25 of the second membrane system 24 enriched in CO2 with respect to the non-permeate 19 is returned to the absorption step 13.
- the non-permeate 26 of the second membrane system 24 sent reforming 2.
- the liquid 34 is distilled off in a distillation column 35 to produce a gas 36 and a carbon dioxide-rich liquid 22.
- the non-permeate 19 of the first system membrane 8 is sent to a second membrane system 24 whose permeate 25 is sent upstream of the compressor 13B and the non-permeate 26 is sent to the reformer 2.
- the second membrane system 24 serves to remove more than 98% of the ethane, propane, propene and benzene in the flow 17 found in the non-permeate 28.
- the non-permeate 19 is condensed to recycle a CO2 enriched condensate 15B to compression 13 and the incondensable 15A passes into a second membrane 24 to separate a hydrogen-rich fraction 26 recycled upstream of the PSA and a fraction 25 rich in carbon monoxide and methane that goes to the reformer burners 2.
- the flow 14 is compressed by the compressor 13A, purified with water (in case the drying is downstream of the PSA) and / or methanol and / or benzene in the adsorber 13C and compressed again by the compressor 13B.
- the flow 17 produced by the compressor 13B is separated to produce a flow enriched in CO2 and depleted in at least one hydrocarbon 20.
- the flow 20 is cooled by the cooler 31, the cooled flow 33 is partially condensed and separated in a separator. phases 32 whose gas 23 is returned to the adsorption 12.
- the liquid 34 is separated by distillation in a distillation column 35 to produce a gas 38 and a liquid rich in carbon dioxide 22. This liquid may contain 99.8% of at least carbon dioxide, being of food grade.
- the non-permeate 19 of the first membrane system 8 is sent to a heat exchanger 37 to partially condense and is separated in a phase separator 15.
- the formed gas 15A is heated in the exchanger 37 and sent to a second membrane system 24 whose permeate 25 is sent upstream of the PSA 12 and the non-permeate 26 is sent to the reformer 2.
- the liquid 15B of the phase separator 15 is expanded and then vaporized in the exchanger 37 to be sent upstream of the compressor 13B
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- General Chemical & Material Sciences (AREA)
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- Hydrogen, Water And Hydrids (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
Description
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FR1761066A FR3073835B1 (fr) | 2017-11-22 | 2017-11-22 | Procede et appareil pour la production combinee d'hydrogene et de dioxyde de carbone a partir d'un melange d'hydrocarbures |
PCT/FR2018/052774 WO2019102094A2 (fr) | 2017-11-22 | 2018-11-08 | Procédé et appareil pour la production combinée d'hydrogène et de dioxyde de carbone à partir d'un mélange d'hydrocarbures |
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EP3713870A2 true EP3713870A2 (fr) | 2020-09-30 |
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KR102212137B1 (ko) | 2016-04-21 | 2021-02-03 | 퓨얼 셀 에너지, 인크 | 이산화탄소 포획을 위해 용융 탄산염 연료 전지 애노드 배기를 후가공처리하는 방법 |
EP3538746A1 (fr) | 2016-11-09 | 2019-09-18 | 8 Rivers Capital, LLC | Systèmes et procédés de production d'énergie à production intégrée d'hydrogène |
KR102651575B1 (ko) | 2017-11-09 | 2024-03-27 | 8 리버스 캐피탈, 엘엘씨 | 수소 및 이산화탄소의 생산 및 분리를 위한 시스템들 및 방법들 |
KR102610181B1 (ko) | 2018-11-30 | 2023-12-04 | 퓨얼셀 에너지, 인크 | 향상된 co2 이용률로 작동되는 연료 전지를 위한 촉매 패턴의 개질 |
US12109527B2 (en) * | 2019-05-30 | 2024-10-08 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Process and apparatus for the separation of two gaseous streams each containing carbon monoxide, hydrogen and at least one acid gas |
KR20220020842A (ko) | 2019-06-13 | 2022-02-21 | 8 리버스 캐피탈, 엘엘씨 | 추가 생성물들의 공동 발생을 구비하는 동력 생산 |
CN110980645A (zh) * | 2019-12-27 | 2020-04-10 | 乔治洛德方法研究和开发液化空气有限公司 | 一种蒸汽烃类重整方法 |
EP4118029A1 (fr) * | 2020-03-11 | 2023-01-18 | Fuelcell Energy, Inc. | Unité de reformage de méthane à la vapeur pour la capture de carbone |
CA3214940A1 (fr) | 2021-04-15 | 2022-10-20 | Iogen Corporation | Procede et systeme de production d'hydrogene renouvelable a faible intensite de carbone |
WO2022221954A1 (fr) | 2021-04-22 | 2022-10-27 | Iogen Corporation | Procédé et système de production de combustible |
FR3125434A1 (fr) * | 2021-07-26 | 2023-01-27 | L'air Liquide Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Procédé et appareil de séparation membranaire d’un mélange contenant comme composants principaux de l’hydrogène et du dioxyde de carbone |
CA3238610A1 (fr) | 2021-11-18 | 2023-05-25 | Rodney John Allam | Appareil de production d'hydrogene |
US11807530B2 (en) | 2022-04-11 | 2023-11-07 | Iogen Corporation | Method for making low carbon intensity hydrogen |
FR3139478A1 (fr) * | 2022-09-08 | 2024-03-15 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Procédé et appareil de séparation membranaire d’un mélange contenant majoritairement de l’hydrogène et du dioxyde de carbone |
FR3139477A1 (fr) * | 2022-09-12 | 2024-03-15 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Procédé de séparation |
FR3141077B1 (fr) * | 2022-10-19 | 2024-09-06 | Air Liquide | Procédé et appareil de séparation d’un mélange d’hydrogène et de dioxyde de carbone |
EP4420753A1 (fr) * | 2023-02-21 | 2024-08-28 | Linde GmbH | Procédé et installation pour fournir une fraction d'hydrogène |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
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FR2877939B1 (fr) | 2004-11-16 | 2007-02-02 | Air Liquide | Procede et installation pour la production combinee d'hydrogene et de dioxyde de carbone |
WO2008016361A1 (fr) * | 2006-08-03 | 2008-02-07 | Utc Fuel Cells, Llc | Traitement de combustible de charge d'alimentation ayant des concentrations en oléfine élevées |
FR2904780B1 (fr) | 2006-08-10 | 2009-10-09 | Air Liquide | Procede de separation d'un gaz de synthese contenant de l'hydrogene et du monoxyde de carbone mais aussi au moins du dioxyde de carbone et de la vapeur d'eau |
EP2366447B1 (fr) * | 2007-03-29 | 2014-12-17 | Nippon Oil Corporation | Procédé et appareil pour la production d'hydrogène et la récupération de dioxyde de carbone |
GB0901472D0 (en) * | 2009-01-30 | 2009-03-11 | Johnson Matthey Plc | Hydrogen process |
FR2953505B1 (fr) * | 2009-12-03 | 2012-02-10 | Air Liquide | Procede pour une production d'hydrogene combinee a une capture de dioxyde de carbone |
EP2873939B1 (fr) * | 2013-11-19 | 2019-02-27 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Procédé et appareil pour la production de CO et CO2 |
-
2017
- 2017-11-22 FR FR1761066A patent/FR3073835B1/fr active Active
-
2018
- 2018-11-08 US US16/765,588 patent/US11554955B2/en active Active
- 2018-11-08 EP EP18867317.2A patent/EP3713870B1/fr active Active
- 2018-11-08 WO PCT/FR2018/052774 patent/WO2019102094A2/fr unknown
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WO2019102094A3 (fr) | 2019-07-25 |
US20200307997A1 (en) | 2020-10-01 |
US11554955B2 (en) | 2023-01-17 |
FR3073835A1 (fr) | 2019-05-24 |
WO2019102094A2 (fr) | 2019-05-31 |
FR3073835B1 (fr) | 2022-10-21 |
EP3713870B1 (fr) | 2024-05-01 |
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